EP0672688B1 - Aluminiumfreie Monocyclopentadienyl-Metallocenkatalysatoren für Olefinpolymerisation - Google Patents
Aluminiumfreie Monocyclopentadienyl-Metallocenkatalysatoren für Olefinpolymerisation Download PDFInfo
- Publication number
- EP0672688B1 EP0672688B1 EP95200999A EP95200999A EP0672688B1 EP 0672688 B1 EP0672688 B1 EP 0672688B1 EP 95200999 A EP95200999 A EP 95200999A EP 95200999 A EP95200999 A EP 95200999A EP 0672688 B1 EP0672688 B1 EP 0672688B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- radicals
- substituted
- hydrocarbyl
- sub
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
- C08F4/74—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals
- C08F4/76—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
Definitions
- This invention relates to a process using a catalyst system comprising certain transition metal compounds of the Group IV-B metals of the Periodic Table of Elements and an ion-exchange activator compound, for the production of polyolefins, particularly polyethylene, polypropylene, and ethylene- ⁇ -olefin copolymers.
- EP 277003 and EP 277004 disclose ionic metallocene based catalysts obtainable from bis (cyclopentadienyl) derivatives of a Group IV-B metal compound and reagents which will irreversibly react with the Group IV-B metal compounds, and their use in polymerization of olefins.
- EP 129368 discloses monocyclopentadienyl Group IV-B metal compounds which form catalysts with alumoxane, which Group IV-B compounds may have halo ligands and include no heteroatom ligand bonded through the heteroatom to the metal.
- EP 250601 discloses catalysts of bis(cyclopentadienyl) derivatives of Group IV-B metals and alumoxane which include heteroatom ligands bonded through the heteroatom to the metal. Monocycopentadienyl compounds are referred to generically in the claims. EP 250601 does not disclose a cocatalyst other than alumoxane and does not disclose monocyclopentadienyl compounds having a bridge between the heteroatom and the cyclopentadienyl ring.
- EP 418044 discloses catalysts comprising a monocyclopentadienyl or substituted monocyclopentadienyl metal complex containing compound corresponding to the formula: CpMX n + A - , wherein Cp is a single ⁇ 5 cyclopentadienyl or ⁇ 5 -substituted cyclopentadienyl group optionally covalently bonded to M through a substituent; M is a metal of Group IIIB, IVB, VB, VIB, VIII or the Lanthanide Series of the Periodic Table bound in an ⁇ 5 bonding mode to the cyclopentadienyl or substituted cyclopentadienyl group; X is independently each occurrence halo, alkyl, aryl, -NR 2 aroxy or alkoxy of up to 20 carbons, or two or more X groups together form a metallocycle with M; R is alkyl or aryl of up to 10 carbons; n is one or two depending
- Example 1 uses pentamethyl cyclopentadienyl titanium isopropoxide dimethyl which contains a heteroatom in combination with an alkyl ligand.
- the earliest priority document from which EP 418044 claims priority discloses polymerization processes using such catalysts to polymerize a lower ⁇ -olefin (having from 3 to 8 carbon atoms) only at a temperature within the range from 0°C to 100°C and at a pressure within the range from 100 kPa to 3400 kPa.
- the invention seeks to provide a process for producing polyolefin that does not contain an undesirable amount of catalyst residue (or ash content, measured as the non-volatile aluminum and transition metal content).
- Aluminum alkyl-free olefin polymerization catalysts derived from transition metal complexes containing fewer than two cyclopentadiene have been relatively unexplored.
- John Bercaw reported [Organometallics, 1990, 9, 867] the synthesis of a monocyclopentadienyl scandium polymerization catalyst, [Me 2 Si(C 5 Me 4 ) (N-Bu t )ScH(PMe 3 ] 2 .
- This neutral Group III catalyst has a low activity and is very expensive due to the high cost of scandium metal.
- the catalyst is not a substituted monocyclopentadienyl metal complex containing compound corresponding to the formula: CpMX n + A - wherein Cp is a single ⁇ 5 -substituted cyclopentadienyl group covalently bonded to M through a substituent; X is alkyl, aryl or alkoxy of up to 20 carbons; and n is one.
- Group IV-B transition metal component can be a polyalkyl or hydride complex containing fewer than two cyclopentadienyl groups.
- the catalyst system is represented by the general formula: wherein: M is Zr, Hf or Ti and is in its highest formal oxidation state (+4, d 0 complex);
- [A] - is a labile, bulky anion which is a single coordination complex having a plurality of lipophilic radicals covalently coordinated to and shielding a central charge-bearing metal or metalloid core and may be formed when the second component, an activator compound comprising a cation which will irreversibly react with at least one ligand contained in said Group IV-B metal compound and a noncoordinating anion [A] - , is combined with the Group IV-B transition metal component, or 'first component'.
- the cation of the second component reacts with one of the ligands of the first component, thereby generating an ion pair consisting of a Group IV-B metal cation with a formal coordination number of 3 and a valence of +4 and the aforementioned anion, which anion is compatible with and non-coordinating toward the metal cation formed from the first component.
- Illustrative but not limiting examples of cations of the second component include Bronsted acids such as ammonium ions or reducible Lewis acids such as Ag + or ferrocenium ions.
- the anion of the second compound stabilizes the Group IV-B metal cation complex without interfering with the Group IV-B metal cation's or its decomposition product's ability to function as a catalyst and is sufficiently labile to permit displacement by an olefin, diolefin or an acetylenically unsaturated monomer during polymerization.
- Catalyst systems of the invention may be prepared by placing the Group IV-B transition metal component and the ion-exchange component in common solution in a normally liquid alkane or aromatic solvent, which solvent is preferably suitable for use as a polymerization diluent for the liquid phase polymerization of an olefin monomer.
- Suitable catalysts can also be prepared by reacting the components and adsorbing on a suitable support material (inorganic oxides or polymers, for example) or by allowing the components to react on such support.
- the process of this invention is practiced with that class of ionic catalysts prepared by combining at least two components.
- the first of these is a monocyclopentadienyl derivative of a Group IV-B metal compound containing at least one ligand which will combine with the second component or at least a portion thereof such as a cation portion thereof.
- the second component is an activator, ion-exchange compound comprising a cation which will irreversibly react with at least one ligand contained in said Group IV-B metal compound and a bulky, labile anion which is normally non-coordinating and stable.
- the cation of the second component reacts with one of the ligands of the first component, thereby generating an ion pair consisting of a Group IV-B metal cation with a formal coordination number of 3 and a valence of +4 and the aforementioned anion, which anion is compatible with and non-coordinating towards the metal cation formed from the first component.
- the anion of the second compound stabilizes the Group IV-B metal cation complex without interfering with the Group IV-B metal cation's or its decomposition product's ability to function as a catalyst and is sufficiently labile to permit displacement by an olefin, diolefin or an acetylenically unsaturated monomer during polymerization.
- the Group IV-B transition metal component of the catalyst system is represented by the general formula: wherein: M is Zr, Hf or Ti and is in its highest formal oxidation state (+4, d 0 complex);
- Exemplary hydrocarbyl radicals for the Q are methyl, ethyl, propyl. butyl, amyl, isoamyl. hexyl, Isobutyl, heptyl, octyl, nonyl, decyl, cetyl, 2-ethylhexyl or phenyl, with methyl being preferred.
- Exemplary substituted hydrocarbyl radicals include trifluoromethyl, pentafluorphenyl, trimethylsilylmethyl, and trimethoxysilylmethyl.
- Exemplary hydrocarbyl substituted metalloid radicals include trimethylsilyl, trimethylgermyl or triphenylsilyl.
- alkyldiene radicals for both Q together are methylidene, ethylidene and propylidene.
- Q group which are suitable as a constituent group or element of the Group IV B transition metal component of the catalyst system are identified in Column 4 of Table 1 under the heading "Q".
- Suitable hydrocarbyl and substituted hydrocarbyl radicals which may be substituted as an R group for at least one hydrogen atom in the cyclopentadienyl ring, will contain from 1 to 20 carbon atoms and include straight and branched alkyl radicals, cyclic hydrocarbon radicals, alkyl-substituted cyclic hydrocarbon radicals, aromatic radicals and alkyl-substituted aromatic radicals.
- Suitable organometallic radicals which may be substituted as an R group for at least one hydrogen atom in the cyclopentadienyl ring, include trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl and trimethylgermyl.
- Examples of cyclopentadienyl ring groups (C 5 H 5-y-x R x ) which are suitable as a constituent group of the Group IV-B transition metal component of the catalyst system are identified in Column 2 of Table 1 under the heading (C 5 H 5-y-x R x ).
- Suitable hydrocarbyl and substituted hydrocarbyl radicals which may be substituted as an R' group for at least one hydrogen atom in the heteroatom J ligand group, will contain from 1 to 20 carbon atoms and include straight and branched alkyl radicals, cyclic hydrocarbon radicals, alkyl-substituted cyclic hydrocarbon radicals, aromatic radicals and alkyl-substituted aromatic radicals.
- heteroatom ligand groups JR' z-l-y
- heteroatom ligand groups which are suitable as a constituent group of the Group IV B transition metal component of the catalyst system are identified in Column 3 of Table 1 under the heading (JR' z-l-y ).
- Table 1 depicts representative constituent moieties for the "Group IV-B transition metal component", the list is for illustrative purposes only and should not be construed to be limiting in any way. A number of final components may be formed by permuting all possible combinations of the constituent moieties with each other.
- Illustrative compounds are: dimethylsilyltetramethylcyclopentadienyl- tert -butylamido zirconium dimethyl, dimethylsilyltetramethylcyclopentadienyl- tert -butylamido hafnium diethyl, dimethylsilyl- tert -butylcyclopentadienyl- tert -butylamido zirconium dihydride, dimethylsilyl- tert -butylcyclopentadienyl- tert -butylamido hafnium diphenyl, dimethylsilyltrimethylsilylcydopentadienyl- tert -butylamido zirconium dihydride, dimethylsilyltetramethylcydopentadienylphenylamido titanium dimethyl, dimethylsilyltetramethylcyclopentadienylphenylamido hafn
- the above compounds and those permuted from Table 1 do not include the neutral Lewis base ligand (L).
- the conditions under which complexes containing neutral Lewis base ligands such as ether or those which form dimers is determined by the steric bulk of the ligands about the metal center.
- a preferred method of preparing these compounds is by reacting a cyclopentadienyl lithium compound with a dihalo-compound whereupon a lithium halide salt is liberated and a monohalo substituent becomes covalently bound to the cyclopentadienyl compound.
- the so substituted cyclopentadienyl reaction product is next reacted with a lithium salt of a phosphide, oxide, sulfide or amide (for the sake of illustration, a lithium amide) whereupon the halo element of the monohalo substituent group of the reaction product reacts to liberate a lithium halide salt and the amine moiety of the lithium amide salt becomes covalently bound to the substituent of the cyclopentadienyl reaction product.
- a lithium salt of a phosphide, oxide, sulfide or amide for the sake of illustration, a lithium amide
- the resulting amine derivative of the cyclopentadienyl product is then reacted with an alkyl lithium reagent whereupon the labile hydrogen atoms, at the carbon atom of the cyclopentadienyl compound and at the nitrogen atom of the amine moiety covalently bound to the substituent group, react with the alkyl of the lithium alkyl reagent to liberate the alkane and produce a dilithtum salt of the cyclopentadienyl compound.
- the bridged species of the Group IV-B transition metal compound is produced by reacting the dilithium salt cyclopentadienyl compound with a Group IV-B transition metal preferably a Group IV-B transition metal halide.
- Unbridged species of the Group IV-B transition metal compound can be prepared from the reaction of a cyclopentadienyl lithium compound and a lithium salt of an amine with a Group IV-B transition metal halide.
- bridged Group IV B transition metal compounds examples include dimethylsilyl, methylphenylsilyl, diethylsilyl, ethylphenylsilyl, diphenylsilyl, ethylene or methylene bridged compounds. Most preferred of the bridged species are dimethylsilyl, diethylsilyl and methylphenylsilyl bridged compounds.
- Compounds useful as an activator component in the preparation of the catalyst used in the process of this invention will comprise a cation, which may be a Bronsted acid capable of donating a proton, and an anion which is normally compatible, noncoordinating, bulky, capable of stabilizing the active catalyst species (the Group IV-B cation) which is formed when the two compounds are combined and which is sufficiently labile to be displaced by olefinic, diolefinic and acetylenically unsaturated substrates or other neutral Lewis bases such as ethers. nitriles and the like.
- Such compatible non-coordinating anions have been disclosed in our European Patent Application 277,004: anionic single coordination complexes comprising a plurality of lipophilic radicals covalently coordinated to and shielding a central charge-bearing metal or metalloid core.
- activator compounds containing single anionic coordination complexes which are useful in this invention may be represented by the following general formula: 5. [(L'-H) + ] d [(M') m+ Q 1 Q 2 ...Q n ] d- wherein:
- any metal or metalloid capable of forming an anionic complex which is stable in water may be used or contained in the anion of the second compound.
- Suitable metals include, but are not limited to, aluminum, gold and platinum.
- Suitable metalloids include, but are not limited to, boron, phosphorus and silicon.
- Compounds containing anions which comprise coordination complexes containing a single metal or metalloid atom are, of course, well known and many, particularly such compounds containing a single boron atom in the anion portion, are available commercially. In light of this, salts containing anions comprising a coordination complex containing a single boron atom are preferred.
- the preferred activator compounds comprising boron may be represented by the following general formula: 5A. [(L'-H) + [BAr 1 Ar 2 X 3 X 4 ] - wherein:
- Ar 1 and Ar 2 may, independently, be any aromatic or substituted-aromatic hydrocarbon radical containing from 6 to 20 carbon atoms.
- Suitable aromatic radicals include, but are not limited to, phenyl. naphthyl and anthracenyl radicals.
- Suitable substituents on the substituted-aromatic hydrocarbon radicals include, but are not necessarily limited to, hydrocarbyl radicals, organometalloid radicals, alkoxy radicals, alkylamido radicals, fluoro and fluorohydrocarbyl radicals such as those useful as X 3 and X4.
- the substituent may be ortho, meta or para, relative to the carbon atoms bonded to the boron atom.
- each may be the same or a different aromatic or substituted-aromatic radical as are Ar 1 and Ar 2 , or the same may be a straight or branched alkyl, alkenyl or alkynyl radical having from 1 to 20 carbon atoms, a cyclic hydrocarbon radical having from 5 to 8 carbon atoms or an alkyl-substituted cyclic hydrocarbon radical having from 6 to 20 carbon atoms.
- X 3 and X 4 may also, independently, be alkoxy or dialkylamido radicals wherein the alkyl portion of said alkoxy and dialkylamido radicals contain from 1 to 20 carbon atoms, hydrocarbyl radicals and organometalloid radicals having from 1 to 20 carbon atoms.
- Ar 1 and Ar 2 may be linked to each other.
- either or both of Ar 1 and Ar 2 could be linked to either X 3 or X 4 .
- X 3 or X 4 may also be linked to each other through a suitable bridging group.
- the catalyst systems employed in the process of the invention comprise a complex formed upon admixture of the Group IV-B transition metal component with the activator component.
- the catalyst system may be prepared by addition of the requisite Group IV-B transition metal and activator components to an inert solvent in which olefin polymerization can be carried out by a solution polymerization procedure.
- the catalyst system may be conveniently prepared by placing the selected Group IV-B transition metal component and the selected activator component, in any order of addition, in an alkane or aromatic hydrocarbon solvent -- preferably toluene.
- the catalyst system may be separately prepared, in concentrated form, and added to the polymerization diluent in a reactor.
- the components of the catalyst system may be prepared as separate solutions and added to the polymerization diluent in a reactor, in appropriate ratios, as is suitable for a continuous liquid polymerization reaction procedure.
- Alkane and aromatic hydrocarbons suitable as solvents for formation of the catalyst system and also as a polymerization diluent are exemplified by, but are not necessarily limited to, straight and branched chain hydrocarbons such as isobutene, butane, pentane, hexane, heptane and octane, cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane and methylcycloheptane, and aromatic and alkyl-substituted aromatic compounds such as benzene, toluene and xylene.
- Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, butene and 1-hexene.
- the Group IV-B transition metal compound is present in the polymerization diluent in concentration of from 0.01 to 1.0 millimoles/liter of diluent and the activator component is present in an amount to provide a molar ratio of the transition metal to activator component from 1:1 to 200:1.
- Sufficient solvent should be employed so as to provide adequate heat transfer away from the catalyst components during reaction and to permit good mixing.
- the catalyst system ingredients that is, the Group IV-B transition metal and activator components, and polymerization diluent can be added to the reaction vessel rapidly or slowly.
- the temperature maintained during the contact of the catalyst components can vary widely, such as, for example, from -10° to 300°C. Greater or lesser temperatures can also be employed.
- the reaction is maintained within is a temperature of from 25° to 100°C, most preferably 25°C.
- the individual catalyst system components, as well as the catalyst system once formed are protected from oxygen and moisture. Therefore, the reactions are performed in an oxygen and moisture free atmosphere and, where the catalyst system is recovered separately, it is recovered in an oxygen and moisture free atmosphere. Preferably, therefore, the reactions are performed in the presence of an inert dry gas such as, for example, helium or nitrogen.
- an inert dry gas such as, for example, helium or nitrogen.
- the overall catalytic performance of the catalyst depends on the choice of metal, the specific (CN)-ligand set, the structure and stability of A-, and the coordinating ability of the cation or Lewis base L'.
- the cation is a proton donor and the Q-ligand of the transition metal component is chosen so that: 1) the metal complex is easy to prepare and is low cost; 2) (CN)MQ 2 is sufficiently basic to deprotonate the acidic cation of the activator component; and 3) Q-H is an unreactive biproduct such as an alkane so that the activation reaction is irreversible.
- the L' and A - portions of the activator component "tune" the stability and overall performance of the catalyst system.
- L' and A - to modify the behavior of a catalyst site increases the versatility of the polymerization system which is an important advantage over conventional methods of activation (e.g. methylalumoxane, and other aluminum alkyl cocatalysts).
- transition metal components identified above may be combined with most activator components identified above to produce an active olefin polymerization catalyst, it is important for continuity of the polymerization operations that either the metal cation initially formed from the first component or a decomposition product thereof be stable. It is also important that the anion of the activator compound be stable to hydrolysis when an ammonium salt is used. Further, it is important that the positive charge of the activator component be sufficient, relative to the metal component, to facilitate the needed cation, e.g., proton transfer. Activator compounds containing aryl-ammonium salts such as N,N-dimethylantlium are more acidic than trialkylammonium salts and therefore are useful with a wider variety of transition metal components. The basicity of the metal complex must also be sufficient to facilitate the needed proton transfer. In general, transition metal compounds which can be hydrolysed by aqueous solutions can be considered suitable as metallocene components to form the catalysts described herein.
- the two compounds combined for preparation of the active catalyst must be selected so as to avoid transfer of a fragment of the anion to the metal cation, thereby forming a catalytically inactive species. This could be done by steric hindrance, resulting from substitutions on the Cp- and/or J-ligands of the first component, as well as substitutions on the non-coordinating anion.
- non-coordinating anion is an anionic coordination complex, such as a tetraphenylboron derivative
- substitutions on the phenyl rings can be used to prevent the transfer of a proton or an entire phenyl group from the anion to the metal. This can be accomplished by alkyl substitution in the ortho positions of the phenyl groups, or, more preferably, by perfluoro-substitutions on the anion.
- anionic coordination complexes containing perfluorophenyl-, trifluoromethylphenyl-, or bis-trifluormethylphenyl rings are preferred for this subgenus of activator components.
- the NMR data clearly suggest that the amine is indeed coordinated to the zirconium atom, but that it is fluxional and probably has two orientations of coordination, most likely in the form of rotational isomers.
- the ionic catalysts species can be crystallized out at -40°C giving a pale powder.
- the solid state NMR spectrum of this material revealed amine coordination to the zirconium atom with more than one orientation.
- the catalyst system is utilized in a liquid phase polymerization of an olefin monomer.
- the liquid phase process comprises the steps of contacting an olefin monomer with the catalyst system in a suitable polymerization diluent and reacting said monomer in the presence of said catalyst system for a time and at a temperature sufficient to produce a polyolefin.
- the monomer for such process may comprise ethylene alone, for the production of a homopolyethylene, or ethylene in combination with an ⁇ -olefin having 3 to 18 carbon atoms for the production of an ethylene- ⁇ -olefin copolymer.
- Conditions for the homo- or copolymerization of ethylene are those wherein ethylene is submitted to the reaction zone at pressures of from 0.0013 bar (0.019 psi) to 3445 bar (50,000 psi) and the reaction temperature is maintained at from -100°C to 300°C, preferably -10° to 220°C, with the proviso that when used to polymerize a lower ⁇ -olefin having from 3 to 8 carbon atoms at a temperature within the range from 0°C to 100°C and at a pressure within the range from 100 kPa to 3400 kPa, the catalyst is not a substituted monocyclopentadienyl metal complex containing compound corresponding to the formula: CpMX n + A - wherein Cp is a single ⁇ 5 -substituted cyclpentadienyl group covalently bonded to M through a substituent; X is alkyl or alkoxy of up to 20 carbons; and n is one.
- one means for carrying out the process of the present invention is as follows: in a stirred-tank reactor liquid 1-butene monomer is introduced.
- the catalyst system is introduced via nozzles in either the vapor or liquid phase.
- Feed ethylene gas is introduced either into the vapor phase of the reactor, or sparged into the liquid phase as is well known in the art.
- the reactor contains a liquid phase composed substantially of liquid 1-butene together with dissolved ethylene gas, and a vapor phase containing vapors of all monomers.
- the reactor temperature and pressure may be controlled via reflux of vaporizing ⁇ -olefin monomer (autorefrigeration), as well as by cooling coils, jackets, etc.
- the polymerization rate is controlled by the rate of catalyst addition, or by the concentration of catalyst.
- the ethylene content of the polymer product is determined by the ratio of ethylene to 1-butene in the reactor, which is controlled by manipulating the relative feed rates of these components to the reactor.
- lithiated substituted cyclopentadienyl compounds are typically prepared from the corresponding cyclopentadienyl ligand and BuLi or MeLi, or by reaction of MeLi with the proper solvene.
- ZrCl 4 and HfCl 4 were purchased from either Aldrich Chemical Company or Cerac.
- Amines, silane and lithium reagents were purchased from Aldrich Chemical Company or Petrarch Systems.
- Activator components were prepared by known literature methods.
- Me 2 Si(Me 4 C 5 )(N- t -Bu)ZrCl 2 (1.07 g, 0.0026 mole) was recovered. Additional Me 2 Si(Me 4 C 5 )(N- t -Bu)ZrCl 2 was recovered from the filtrate by repeating the recrystallization procedure. Total yield, 1.94 g, 0.0047 mol).
- Me 2 Si(C 5 Me 4 )(N- t -Bu)ZrMe 2 was prepared by adding a stoichiometric amound of MeLi (1.4 M in ether) to Me 2 Si(C 5 Me 4 )(N- t -Bu)ZrCl 2 suspended in ether. The white solid was isolated in an 83% yield.
- MePhSiCl 2 (14.9 g, 0.078 mol) was diluted with ⁇ 250 ml of thf.
- Me 4 C 5 HLi (10.0 g. 0.078 mol) was slowly added as a solid.
- the reaction solution was allowed to stir overnight.
- the solvent was removed via a vacuum to a cold trap held at -196°C. Petroleum ether was added to precipitate out the LiCl.
- the mixture was filtered through Celite, and the pentane was removed from the filtrate.
- MePhSi(Me 4 C 5 H)Cl (20.8 g, 0.075 mol) was isolated as a yellow viscous liquid.
- MePhSi(Me 4 C 5 )(N- t -Bu)HfMe 2 was prepared by adding a stoichiometric amount of HeLi (1.4 M in ether) to MePhSi(Me 4 C 5 )(N- t -Bu)HfCl 2 suspended in ether. The white solid could be isolated in near quantitative yield.
- a catalyst solution prepared from 19.7 mg of Me 2 Si(Me 4 C 5 )(N- t -Bu)ZrMe 2 and 6 mg of [DMAH] [B(pfp) 4 ] in 20 mls of toluene was added to a 1 liter stainless-steel autoclave containing 400 mls of hexane.
- the reactor temperature was maintained at 40°C and stirred vigorously while ethylene was added at 6.2 bar (90 psi). After 30 minutes the reaction was stopped giving 30 grams of HDPE after work-up.
- the GPC analysis showed a bimodal distribution with modes centered at 900,000 and 2,000.
- a catalyst solution prepared from 28.6 mg of Me 2 Si(Me 4 C 5 )(N- t -Bu)ZrMe 2 and 9 mg of [DMAH] [B(pfp)] 4 in 20 mls of toluene was added to a 1 liter stainless-steel autoclave containing 400 mls of hexane.
- the reactor temperature was set at 50°C and was stirred vigorously while 100 mls of butene and 4.1 bar (60 psi) of ethylene were added. Following the addition of butene and ethylene, an instantaneous increase in temperature to 90°C was observed. After 30 minutes the reaction was stopped, yielding 130 grams of a waxy ethylene-butene copolymer.
- GPC analysis showed a bimodal distribution with modes centered at 27,000 and 2,000 in approximately equal ratios.
- IR spectroscope showed the presence of butene in the copolymer.
- a catalyst solution prepared from 40 mg of MePhSi(C 5 Me 4 )(N- t -Bu)HfMe 2 and 11 mg of [DMAH][B(pfp 4 ] in 20 mls of toluene was added to a 1 liter autoclave containing 400 mls of hexane.
- the reactor temperature was set at 40°C, stirred vigorously and pressurized with ethylene 4.1 bar (90 psi) for 15 minutes.
- the reactor temperature increased from 40 to 97°C during the polymerization.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Claims (16)
- Verfahren zur Homo- oder Copolymerisation von Ethylen, bei dem Ethylen einer Reaktionszone mit einem Druck von 0,0013 bar bis 3445 bar und einer Temperatur von -100 bis 300°C zugeführt wird, wobei ein Katalysatorsystem mit der folgenden Formel verwendet wird(C5H5-y-xRx) ein Cyclopentadienylring ist, der mit null bis fünf Substituentengruppen R substituiert ist, "x" 0, 1, 2, 3, 4 oder 5 ist und den Substitutionsgrad bezeichnet und jede Substituentengruppe R unabhängig ein Rest ausgewählt aus einer Gruppe bestehend aus C1- bis C20-Kohlenwasserstoffresten, substituierten C1- bis C20-Kohlenwasserstoffresten, bei denen ein oder mehrere Wasserstoffatome durch ein Halogenatom ersetzt sind, mit C1- bis C20-Kohlenwasserstoff substituierten Metalloidresten, bei denen das Metalloid ausgewählt ist aus der Gruppe IV A des Periodensystems der Elemente, und Halogenresten ist, oder (C5H5-y-xRx) ein Cyclopentadienylring ist, in dem zwei benachbarte R-Gruppen unter Bildung eines C4- bis C20-Rings verbunden sind, um einen polycyclischen Cyclopentadienylliganden zu ergeben;(JR'z-l-y) ein Heteroatomligand ist, in dem J ein Element mit einer Koordinationszahl von drei aus der Gruppe V-A oder ein Element mit einer Koordinationszahl von zwei aus der Gruppe VI-A des Periodensystems der Elemente ist und jedes R' unabhängig ein Rest ausgewählt aus einer Gruppe bestehend aus C1- bis C20-Kohlenwasserstoffresten und substituierten C1- bis C20-Kohlenwasserstoffresten, in denen ein oder mehrere Wasserstoffatome durch ein Halogenatom ersetzt sind, ist, und "z" die Koordinationszahl des Elements J ist,jedes Q unabhängig Hydrid, C1- bis C50-Kohlenwasserstoffreste, substituierte Kohlenwasserstoffreste, in denen ein oder mehrere Wasserstoffatome durch eine elektronenanziehende Gruppe wie ein Halogenatom oder einen Alkoxidrest ersetzt sind, oder mit C1- bis C50-Kohlenwasserstoff substituierte Metalloidreste sein kann, in denen das Metalloid ausgewählt ist aus der Gruppe IV-A des Periodensystems der Elemente mit der Maßgabe, daß, wenn irgendein Q ein Kohlenwasserstoff ist, dieses Q sich von (C5H5-y-xRx) unterscheidet, oder beide Q zusammen ein Alkyliden, Olefin, Acetylen oder cyclometallierter Kohlenwasserstoffrest sein können,"y" 0 oder 1 ist; wenn "y" 1 ist, B eine kovalente Brückengruppe ist, die ein Gruppe-IV-A- oder -V-A-Element enthält,L eine neutrale Lewisbase ist und "w" eine Zahl von 0 bis 3 ist, und[A]- ein labiles raumerfüllendes Anion ist, das ein einziger Koordinationskomplex mit mehreren lipophilen Resten ist, die kovalent um ein ladungstragendes Metall- oder Metalloidrentrum koordiniert sind und dieses abschirmen, mit der Maßgabe, daß bei Verwendung zum Polymerisieren eines niedrigeren α-olefins mit 3 bis 8 Kohlenstoffatomen bei einer Temperatur im Bereich von 0°C bis 100°C und einem Druck im Bereich von 100 kPa bis 3400 kPa der Katalysator kein substituierter Monocyclopentadienyl-Metall-Komplex ist, der eine Verbindung entsprechend der Formel CpMXn +A- enthält, in der Cp eine einzige η5-substituierte Cyclopentadienylgruppe ist, die über einen Substituenten kovalent an M gebunden ist, X Alkyl, Aryl oder Alkoxy mit bis zu 20 Kohlenstoffatomen ist und n eins ist.
- Verfahren nach Anspruch 1, in dem das Katalysatorsystem getrennt in konzentrierter Form hergestellt und einem Polymerisationsverdünnungsmittel zugegeben wird, oder bei dem das katalysatorsystem in situ in einem Polymerisationsverdünnungsmittel in dem Reaktor gebildet wird.
- Verfahren nach Anspruch 1, bei dem das Katalysatorsystem auf einem Träger adsorbiert ist.
- Verfahren nach Anspruch 1, bei dem in Stufen Ethylen entweder allein oder in Kombination mit anderen Olefinen und/oder anderen ungesättigten Monomeren in einem geeigneten Polymerisationsverdünnungsmittel mit dem Katalysatorsystem kontaktiert wird.
- Verfahren nach Anspruch 2, bei dem die Reaktionstemperatur auf -10 bis 220°C gehalten wird.
- Verfahren nach Anspruch 1, bei dem die Polymerisation in der flüssigen Phase erfolgt.
- Verfahren nach einem der Ansprüche 1 bis 6, bei dem das Element der Heteroatomligandengruppe Stickstoff, Phosphor, Sauerstoff oder Schwefel ist.
- Verfahren nach Anspruch 7, bei dem y=1 ist und B eine lineare, verzweigte oder cyclische Alkylengruppe mit 1 bis 6 Kohlenstoffatomen, eine alkylsubstituierte Silaalkylengruppe mit 1 bis 2 Siliciumatomen anstelle der Kohlenstoffatome in der Brücke oder eine Si1-Si2-alkylsubstituierte Silanylengruppe ist.
- Verfahren nach einem der vorhergehenden Ansprüche 1 bis 8, bei dem R' 1 bis 20 Kohlenstoffatome enthält und ein geradkettiger oder verzweigter Alkylrest, cyclischer Kohlenwasserstoffrest, alkylsubstituierter cyclischer Kohlenwasserstoffrest, aromatischer Rest oder ein alkylsubstituierter aromatischer Rest ist.
- Verfahren nach einem der vorhergehenden Ansprüche 1 bis 9, bei dem das Anion substituierte Phenylringe enthält, vorzugsweise einen ortho-alkylsubstituierten Phenylring, oder ein perfluorsubstituiertes Anion ist.
- Verfahren nach einem der vorhergehenden Ansprüche 1 bis 10, das während einer Zeitdauer von 1 Sekunde bis 10 Stunden durchgeführt wird, um ein Polymer mit einem durchschnittlichen Molekulargewicht (Gewichtsmittel) von 1000 bis 5 000 000 und einer Molekulargewichtsverteilung von 1,5 oder höher zu ergeben.
- Verfahren nach Anspruch 1, bei dem C5H5-y-xRx Tetramethylcyclopentadienyl ist.
- Verfahren nach Anspruch 1, bei dem Y=1 ist und B Dimethylsilyl ist.
- Verfahren nach Anspruch 1, bei dem JR'Z-1-y tert.-Butylamid ist.
- Verfahren nach Anspruch 1, bei dem Q Methyl ist.
- Verfahren nach Anspruch 1, bei dem M Titan ist.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/542,236 US7163907B1 (en) | 1987-01-30 | 1990-06-22 | Aluminum-free monocyclopentadienyl metallocene catalysts for olefin polymerization |
US542236 | 1990-06-22 | ||
EP91912554A EP0551277B2 (de) | 1990-06-22 | 1991-06-21 | Aluminiumfreie monocyclopentadienyl-metallocenkatalysatoren für olefinpolymerisation |
Related Parent Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP91912554A Division EP0551277B2 (de) | 1990-06-22 | 1991-06-21 | Aluminiumfreie monocyclopentadienyl-metallocenkatalysatoren für olefinpolymerisation |
EP91912554.2 Division | 1991-06-21 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0672688A1 EP0672688A1 (de) | 1995-09-20 |
EP0672688B1 true EP0672688B1 (de) | 1996-09-18 |
EP0672688B2 EP0672688B2 (de) | 2002-04-17 |
Family
ID=24162910
Family Applications (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP91912554A Expired - Lifetime EP0551277B2 (de) | 1990-06-22 | 1991-06-21 | Aluminiumfreie monocyclopentadienyl-metallocenkatalysatoren für olefinpolymerisation |
EP95200999A Expired - Lifetime EP0672688B2 (de) | 1990-06-22 | 1991-06-21 | Aluminiumfreie Monocyclopentadienyl-Metallocenkatalysatoren für Olefinpolymerisation |
EP95200997A Withdrawn EP0670334A3 (de) | 1990-06-22 | 1991-06-21 | Aluminiumfreie Monocyclopentadienyl-Metallocenkatalysatoren für Olefinpolymerisation |
EP95200998A Withdrawn EP0672689A1 (de) | 1990-06-22 | 1991-06-21 | Aluminiumfreie Monocyclopentadienyl-Metallocenkatalysatoren für Olefinpolymerisation |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP91912554A Expired - Lifetime EP0551277B2 (de) | 1990-06-22 | 1991-06-21 | Aluminiumfreie monocyclopentadienyl-metallocenkatalysatoren für olefinpolymerisation |
Family Applications After (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95200997A Withdrawn EP0670334A3 (de) | 1990-06-22 | 1991-06-21 | Aluminiumfreie Monocyclopentadienyl-Metallocenkatalysatoren für Olefinpolymerisation |
EP95200998A Withdrawn EP0672689A1 (de) | 1990-06-22 | 1991-06-21 | Aluminiumfreie Monocyclopentadienyl-Metallocenkatalysatoren für Olefinpolymerisation |
Country Status (11)
Country | Link |
---|---|
EP (4) | EP0551277B2 (de) |
JP (1) | JP2954351B2 (de) |
KR (1) | KR0123370B1 (de) |
AT (1) | ATE147761T1 (de) |
BR (1) | BR9106589A (de) |
CA (1) | CA2085581C (de) |
DE (3) | DE551277T1 (de) |
DK (1) | DK0551277T4 (de) |
ES (2) | ES2092913T5 (de) |
RU (1) | RU2118203C1 (de) |
WO (1) | WO1992000333A2 (de) |
Families Citing this family (311)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5384299A (en) * | 1987-01-30 | 1995-01-24 | Exxon Chemical Patents Inc. | Ionic metallocene catalyst compositions |
US5763547A (en) * | 1992-10-02 | 1998-06-09 | The Dow Chemical Company | Supported catalyst complexes for olefin in polymerization |
US5064802A (en) † | 1989-09-14 | 1991-11-12 | The Dow Chemical Company | Metal complex compounds |
US6294625B1 (en) | 1990-03-20 | 2001-09-25 | Exxonmobil Chemical Patents Inc. | Catalyst system of enhanced productivity and its use in polymerization process |
US5801113A (en) * | 1990-06-22 | 1998-09-01 | Exxon Chemical Patents, Inc. | Polymerization catalyst systems, their production and use |
KR100236805B1 (ko) * | 1991-10-15 | 2000-02-01 | 그레이스 스티븐 에스. | 금속 배위 착화합물의 제조방법 |
DE69222317T2 (de) * | 1991-11-25 | 1998-02-12 | Exxon Chemical Patents, Inc., Baytown, Tex. | Polyionische, uebergangsmetall enthaltende katalysatorzusammensetzung |
DE69224287T2 (de) * | 1992-01-06 | 1998-08-27 | The Dow Chemical Co., Midland, Mich. | Katalysatorzusammensetzung |
WO1993019103A1 (en) * | 1992-03-16 | 1993-09-30 | Exxon Chemical Patents Inc. | IONIC CATALYST FOR THE PRODUCTION OF POLY-α-OLEFINS OF CONTROLLED TACTICITY |
US6143854A (en) | 1993-08-06 | 2000-11-07 | Exxon Chemical Patents, Inc. | Polymerization catalysts, their production and use |
JP3153000B2 (ja) * | 1992-06-11 | 2001-04-03 | 三菱化学株式会社 | α‐オレフィン重合体の製造法 |
CA2139356C (en) * | 1992-07-01 | 2001-02-06 | Donna J. Crowther | Transition metal olefin polymerization catalysts |
EP1110974B1 (de) * | 1992-08-05 | 2007-11-28 | ExxonMobil Chemical Patents Inc. | Verfahren zur Herstellung von einem geträgertem Aktivatorkomponenten |
CA2145635A1 (en) * | 1992-09-29 | 1994-04-14 | Patrick Brant | Long chain branched polymers and a process to make long chain branched polymers |
US5322728A (en) * | 1992-11-24 | 1994-06-21 | Exxon Chemical Patents, Inc. | Fibers of polyolefin polymers |
US5635573A (en) * | 1992-12-01 | 1997-06-03 | Exxon Chemical Patents Inc. | Method for preparing alpha-olefin/cycloolefin copolymers |
DE69433347T2 (de) * | 1993-01-29 | 2004-04-15 | Dow Global Technologies, Inc., Midland | Ethylen Copolymerisation |
ES2156153T3 (es) | 1993-06-15 | 2001-06-16 | Idemitsu Kosan Co | Procedimiento de produccion de polimero olefinico, y catalizador para la polimerizacion de una olefina. |
JPH09501191A (ja) * | 1993-06-30 | 1997-02-04 | エクソン・ケミカル・パテンツ・インク | 開環複分解重合用の新規な触媒 |
IT1271406B (it) * | 1993-09-13 | 1997-05-28 | Spherilene Srl | Procedimento per la preparazione di polimeri dell'etilene e prodotti ottenuti |
IT1271407B (it) * | 1993-09-13 | 1997-05-28 | Spherilene Srl | Procedimento per la preparazione di copolimeri elastomerici dell'etilene e prodotti ottenuti |
ES2160634T3 (es) | 1993-09-17 | 2001-11-16 | Exxonmobil Chem Patents Inc | Sistemas catalizadores de polimerizacion, su produccion y uso. |
WO1995014024A1 (fr) * | 1993-11-18 | 1995-05-26 | Idemitsu Kosan Co., Ltd. | Compose de metal de transition, catalyseur de polymerisation d'olefines et procede pour produire un polymere d'olefines en utilisant ce catalyseur |
US5504223A (en) * | 1994-01-25 | 1996-04-02 | The Dow Chemical Company | Synthesis of cyclopentadienyl metal coordination complexes from metal hydrocarbyloxides |
US5674950A (en) * | 1994-03-07 | 1997-10-07 | Exxon Chemical Patents Inc. | Polymers having terminal hydroxyl aldehyde, or alkylamino substitutents and derivatives thereof |
US5691422A (en) * | 1994-03-07 | 1997-11-25 | Exxon Chemical Patents Inc. | Saturated polyolefins having terminal aldehyde or hydroxy substituents and derivatives thereof |
US5504224A (en) * | 1994-03-14 | 1996-04-02 | The Dow Chemical Company | Preparation of monocyclopentadienyl metal complexes by nucleophilic substitution of bis(cyclopentadienyl) metal complexes |
US5648438A (en) * | 1994-04-01 | 1997-07-15 | Exxon Chemical Patents, Inc. | Process for producing polymers with multimodal molecular weight distributions |
US6291389B1 (en) | 1994-04-28 | 2001-09-18 | Exxonmobil Chemical Patents Inc. | Cationic polymerization catalysts |
US5936041A (en) * | 1994-06-17 | 1999-08-10 | Exxon Chemical Patents Inc | Dispersant additives and process |
IT1270253B (it) | 1994-06-20 | 1997-04-29 | Spherilene Srl | Copolimeri dell'etilene e procedimento per la preparazione di polimeri dell'etilene |
US5486632A (en) * | 1994-06-28 | 1996-01-23 | The Dow Chemical Company | Group 4 metal diene complexes and addition polymerization catalysts therefrom |
CA2191483C (en) * | 1994-07-11 | 2003-02-25 | Antonio Gutierrez | Lubricating oil succinimide dispersants derived from heavy polyamine |
IT1273662B (it) | 1994-07-20 | 1997-07-09 | Spherilene Srl | Procedimento per la preparazione di polimeri amorfi del propiline' |
US5565128A (en) * | 1994-10-12 | 1996-10-15 | Exxon Chemical Patents Inc | Lubricating oil mannich base dispersants derived from heavy polyamine |
US5625015A (en) | 1994-11-23 | 1997-04-29 | Exxon Chemical Patents Inc. | Method for making supported catalyst systems and catalyst systems therefrom |
US6143682A (en) * | 1995-06-07 | 2000-11-07 | Exxon Chemical Patents Inc. | Bimetallocyclic transition metal catalyst systems |
US5766713A (en) * | 1995-06-14 | 1998-06-16 | Exxon Chemical Patents Inc. | Elastomeric vehicle hoses |
TW338046B (en) * | 1995-06-29 | 1998-08-11 | Ciba Sc Holding Ag | Process for the preparation of stabilized olefin polymers |
EP0842939B1 (de) | 1995-07-14 | 2004-10-06 | Sumitomo Chemical Company, Limited | Übergangsmetallkomplex enthaltender polymerisationskatalysator und verfahren zur herstellung von olefinpolymeren |
WO1997005143A1 (fr) * | 1995-07-25 | 1997-02-13 | Asahi Kasei Kogyo Kabushiki Kaisha | Nouveaux composes a base de metaux de transition du groupe 4 |
US5869575A (en) * | 1995-08-02 | 1999-02-09 | The Dow Chemical Company | Ethylene interpolymerizations |
JPH11510546A (ja) | 1995-08-10 | 1999-09-14 | エクソン・ケミカル・パテンツ・インク | メタロセンで安定化されたアルモキサン |
US5652202A (en) * | 1995-08-15 | 1997-07-29 | Exxon Chemical Patents Inc. | Lubricating oil compositions |
CN1080724C (zh) * | 1995-08-31 | 2002-03-13 | 住友化学工业株式会社 | 过渡金属配合物,烯烃聚合催化剂及生产烯烃聚合物的方法 |
US5558802A (en) * | 1995-09-14 | 1996-09-24 | Exxon Chemical Patents Inc | Multigrade crankcase lubricants with low temperature pumpability and low volatility |
GB9519381D0 (en) | 1995-09-22 | 1995-11-22 | Exxon Chemical Patents Inc | Rubber toughened blends |
JPH11513717A (ja) * | 1995-10-14 | 1999-11-24 | ビーエーエスエフ アクチェンゼゲルシャフト | 高圧下にエチレン共重合体を製造する方法 |
IT1276070B1 (it) | 1995-10-31 | 1997-10-24 | Siac It Additivi Carburanti | Processo per la preparazione di polimeri a base di etilene a basso peso molecolare |
IT1282666B1 (it) | 1996-02-22 | 1998-03-31 | Enichem Spa | Catalizzatore metallocenico sostituito per la (co) polimerizzazione delle olefine |
US5786291A (en) * | 1996-02-23 | 1998-07-28 | Exxon Chemical Patents, Inc. | Engineered catalyst systems and methods for their production and use |
NL1003020C2 (nl) * | 1996-05-03 | 1997-11-06 | Dsm Nv | Cyclopentadieenverbinding met een niet-coördinerend anion. |
US5811379A (en) * | 1996-06-17 | 1998-09-22 | Exxon Chemical Patents Inc. | Polymers derived from olefins useful as lubricant and fuel oil additives, processes for preparation of such polymers and additives and use thereof (PT-1267) |
US6194341B1 (en) | 1996-06-17 | 2001-02-27 | Exxon Chemical Patents Inc. | Mixed transition metal catalyst systems for olefin polymerization |
US6066603A (en) * | 1996-06-17 | 2000-05-23 | Exxon Chemical Patents Inc. | Polar monomer containing copolymers derived from olefins useful as lubricant and useful as lubricant and fuel oil additivies process for preparation of such copolymers and additives and use thereof |
US6759499B1 (en) | 1996-07-16 | 2004-07-06 | Exxonmobil Chemical Patents Inc. | Olefin polymerization process with alkyl-substituted metallocenes |
DE19630580A1 (de) * | 1996-07-30 | 1998-02-05 | Studiengesellschaft Kohle Mbh | Organochrom-Verbindungen enthaltende Katalysatoren und ihre Verwendung in der Alkenpolymerisation |
GB9617507D0 (en) | 1996-08-21 | 1996-10-02 | Exxon Chemical Patents Inc | Chemically modified elastomeres and blends thereof |
US5952427A (en) * | 1996-12-10 | 1999-09-14 | Exxon Chemical Patents Inc. | Electrical devices including ethylene, α-olefin, vinyl norbornene elastomers and ethylene α-olefin polymers |
US5763533A (en) | 1996-12-10 | 1998-06-09 | Exxon Chemical Patents Inc. | Electrical devices including ethylene, α-olefin, vinyl norbornene elastomers and ethylene α-olefin polymers |
EP0853091A1 (de) | 1997-01-13 | 1998-07-15 | Bp Chemicals S.N.C. | Verfahren zur Polymerisation |
EP0958313B1 (de) | 1997-02-07 | 2002-09-25 | ExxonMobil Chemical Patents Inc. | Thermoplastische,elastomere zusammensetzungen aus verzweigten olefincopolymeren |
JP2001511214A (ja) | 1997-02-07 | 2001-08-07 | エクソン・ケミカル・パテンツ・インク | ビニル含有マクロマーの調製 |
US5851945A (en) * | 1997-02-07 | 1998-12-22 | Exxon Chemical Patents Inc. | Olefin polymerization catalyst compositions comprising group 5 transition metal compounds stabilized in their highest metal oxidation state |
US6172015B1 (en) | 1997-07-21 | 2001-01-09 | Exxon Chemical Patents, Inc | Polar monomer containing copolymers derived from olefins useful as lubricant and fuel oil additives, processes for preparation of such copolymers and additives and use thereof |
US7026404B2 (en) | 1997-08-12 | 2006-04-11 | Exxonmobil Chemical Patents Inc. | Articles made from blends made from propylene ethylene polymers |
US6635715B1 (en) | 1997-08-12 | 2003-10-21 | Sudhin Datta | Thermoplastic polymer blends of isotactic polypropylene and alpha-olefin/propylene copolymers |
US6921794B2 (en) | 1997-08-12 | 2005-07-26 | Exxonmobil Chemical Patents Inc. | Blends made from propylene ethylene polymers |
US6100224A (en) * | 1997-10-01 | 2000-08-08 | Exxon Chemical Patents Inc | Copolymers of ethylene α-olefin macromers and dicarboxylic monomers and derivatives thereof, useful as additives in lubricating oils and in fuels |
US6096677A (en) * | 1997-10-17 | 2000-08-01 | Sri International | Supported metallocene catalysts |
US5892079A (en) * | 1997-10-17 | 1999-04-06 | Sri International | Metallocene catalysts and associated methods of preparation and use |
US5986024A (en) * | 1997-10-17 | 1999-11-16 | Sri International | Preparation of multimodal polymer compositions using multinuclear metallocene catalysts |
US6197910B1 (en) | 1997-12-10 | 2001-03-06 | Exxon Chemical Patents, Inc. | Propylene polymers incorporating macromers |
US6117962A (en) * | 1997-12-10 | 2000-09-12 | Exxon Chemical Patents Inc. | Vinyl-containing stereospecific polypropylene macromers |
US6184327B1 (en) | 1997-12-10 | 2001-02-06 | Exxon Chemical Patents, Inc. | Elastomeric propylene polymers |
EP0979232B1 (de) * | 1998-01-14 | 2002-10-09 | Basell Polyolefine GmbH | Verfahren zur herstellung von metallocenen |
WO1999054369A1 (en) | 1998-04-21 | 1999-10-28 | Montell Technology Company B.V. | Process for the preparation of copolymers of ethylene with alpha-olefins |
US6784269B2 (en) | 1998-05-13 | 2004-08-31 | Exxonmobil Chemical Patents Inc. | Polypropylene compositions methods of making the same |
US6306960B1 (en) | 1998-05-13 | 2001-10-23 | Exxonmobil Chemical Patents Inc. | Articles formed from foamable polypropylene polymer |
DE69918100T2 (de) | 1998-05-13 | 2005-07-07 | Exxonmobil Chemical Patents Inc., Baytown | Propylenhomopolymere und herstellungsverfahren |
US6245868B1 (en) | 1998-05-29 | 2001-06-12 | Univation Technologies | Catalyst delivery method, a catalyst feeder and their use in a polymerization process |
DE69935815T2 (de) | 1998-07-01 | 2007-12-27 | Exxonmobil Chemical Patents Inc., Baytown | Elastische Mischung mit Kristallpolymeren und kristallisierbaren Polymeren des Propens |
JP2002519484A (ja) | 1998-07-02 | 2002-07-02 | モンテル テクノロジー カンパニー ビーブイ | 実質的非晶質α−オレフィンポリマーの製造法とそれを含有する組成物および橋状リガンドの製造法 |
CA2336811A1 (en) | 1998-07-10 | 2000-01-20 | Joann M. Canich | Tethered monocyclopentadienyl polymerization catalysts |
IT1301990B1 (it) | 1998-08-03 | 2000-07-20 | Licio Zambon | Catalizzatori per la polimerizzazione delle olefine. |
JP5407099B2 (ja) | 1998-08-26 | 2014-02-05 | エクソンモービル・ケミカル・パテンツ・インク | 分枝ポリプロピレン組成物 |
US6403773B1 (en) | 1998-09-30 | 2002-06-11 | Exxon Mobil Chemical Patents Inc. | Cationic group 3 catalyst system |
US6087515A (en) | 1998-10-07 | 2000-07-11 | Solvay Polyolefins Europe-Belgium (Societe Anonyme) | Metallocenes and process for the preparation of metallocenes |
KR100548614B1 (ko) * | 1998-10-20 | 2006-06-07 | 에스케이 주식회사 | 폴리에틸렌 제조용 메탈로센 촉매 및 이를 이용한 폴리에틸렌의제조방법 |
US6486088B1 (en) | 1998-10-23 | 2002-11-26 | Exxonmobil Chemical Patents Inc. | High activity carbenium-activated polymerization catalysts |
AU2020400A (en) | 1998-10-29 | 2000-05-22 | Exxon Chemical Patents Inc. | Ethylene alpha-olefin elastomeric polymer compositions having improved extrusionprocessibility |
US6281289B1 (en) | 1998-12-08 | 2001-08-28 | The Dow Chemical Company | Polypropylene/ethylene polymer fiber having improved bond performance and composition for making the same |
US6174930B1 (en) | 1999-04-16 | 2001-01-16 | Exxon Chemical Patents, Inc. | Foamable polypropylene polymer |
US6339134B1 (en) * | 1999-05-06 | 2002-01-15 | Univation Technologies, Llc | Polymerization process for producing easier processing polymers |
US6479598B1 (en) | 1999-07-20 | 2002-11-12 | Exxonmobil Chemical Patents Inc. | Petroleum resins and their production with BF3 catalyst |
IT1313599B1 (it) * | 1999-08-05 | 2002-09-09 | Enichem Spa | Complessi metallici utilizzabili nella catalisi per la (co)polimerizzazione delle alfa-olefine |
US6444302B1 (en) | 1999-09-01 | 2002-09-03 | Exxonmobil Chemical Patents Inc. | Breathable films and method for making |
US6403743B1 (en) | 1999-09-14 | 2002-06-11 | Exxonmobil Chemical Patents Inc. | Petroleum resins and their production with supported catalyst |
US6544919B1 (en) | 1999-10-06 | 2003-04-08 | Sri International | Multinuclear transition metal catalysts for preparation of multimodal polymer compositions |
US6476164B1 (en) | 1999-10-22 | 2002-11-05 | Exxonmobil Chemical Patents Inc. | Carbenium cationic complexes suitable for polymerization catalysts |
US6475946B1 (en) | 1999-10-22 | 2002-11-05 | Exxonmobil Chemical Patents Inc. | Olefin polymerization catalysis with aryl substituted carbenium cationic complexes |
US6559090B1 (en) | 1999-11-01 | 2003-05-06 | W. R. Grace & Co.-Conn. | Metallocene and constrained geometry catalyst systems employing agglomerated metal oxide/clay support-activator and method of their preparation |
EP1226206B1 (de) | 1999-11-04 | 2003-10-22 | ExxonMobil Chemical Patents Inc. | Propylencopolymerschäume und deren verwendung |
US6822057B2 (en) | 1999-12-09 | 2004-11-23 | Exxon Mobil Chemical Patents Inc. | Olefin polymerization catalysts derived from Group-15 cationic compounds and processes using them |
US6489480B2 (en) | 1999-12-09 | 2002-12-03 | Exxonmobil Chemical Patents Inc. | Group-15 cationic compounds for olefin polymerization catalysts |
US6281306B1 (en) | 1999-12-16 | 2001-08-28 | Univation Technologies, Llc | Method of polymerization |
CA2393327A1 (en) | 1999-12-20 | 2001-06-28 | Exxon Chemical Patents Inc. | Processes for the preparation polyolefin resins using supported ionic catalysts |
JP2003518530A (ja) | 1999-12-28 | 2003-06-10 | バセル テクノロジー カンパニー ビー.ブイ. | エチレンポリマー類の製造方法 |
DE60045930D1 (de) | 1999-12-28 | 2011-06-16 | Basell Polyolefine Gmbh | Heterocyclische Metallocene und ihre Verwendung in Katalysatorsystemen zur Herstellung von Olefin Polymeren |
JP2003518531A (ja) | 1999-12-28 | 2003-06-10 | バセル テクノロジー カンパニー ビー.ブイ. | エチレンポリマーの製造方法 |
KR100645631B1 (ko) * | 2000-02-10 | 2006-11-13 | 에스케이 주식회사 | 폴리에틸렌 제조용 메탈로센 촉매, 이의 제조방법 및 이를이용한 중합방법 |
ES2223832T3 (es) | 2000-03-22 | 2005-03-01 | Basell Polyolefine Gmbh | Procedimiento para la preparacion de composiciones termoplasticas de propileno isotactico y polipropileno flexible de isotacticidad inferior. |
US6809209B2 (en) | 2000-04-07 | 2004-10-26 | Exxonmobil Chemical Patents Inc. | Nitrogen-containing group-13 anionic compounds for olefin polymerization |
US6635733B2 (en) | 2000-05-23 | 2003-10-21 | Chisso Corporation | Elastomeric polypropylene |
US6846943B2 (en) | 2000-05-23 | 2005-01-25 | Chisso Corporation | Metallocene compound, olefin polymerization catalyst containing the compound, and method for producing an olefin polymer by use of the catalyst |
ITMI20012085A1 (it) | 2000-10-17 | 2003-04-09 | Ciba Sc Holding Ag | Polpropilene metallocene stabilizzato |
JP2004516365A (ja) | 2000-12-22 | 2004-06-03 | バセル ポリオレフィン イタリア エス.ピー.エー. | 多孔性ポリマーの製造方法およびそれから得られるポリマー |
EP1401887A1 (de) | 2001-04-30 | 2004-03-31 | W.R. Grace & Co.-Conn. | Heterogene chromkatalysatoren und verfahren zur polymerisation von olefinen mit diesen katalysatoren |
WO2002102859A2 (en) | 2001-04-30 | 2002-12-27 | W. R. Grace & Co.-Conn. | Coordination catalyst systems employing chromium support-agglomerate and method of their preparation |
WO2002088200A1 (en) | 2001-04-30 | 2002-11-07 | W.R. Grace & Co.-Conn. | Supported dual transition metal catalyst systems |
US6943224B2 (en) | 2001-04-30 | 2005-09-13 | W. R. Grace & Co.-Conn. | Process for preparing supported transition metal catalyst systems and catalyst systems prepared thereby |
US6927261B2 (en) | 2001-04-30 | 2005-08-09 | W. R. Grace & Co.-Conn. | Method of making supported transition metal polymerization catalysts and compositions formed therefrom |
ATE519789T1 (de) | 2001-06-12 | 2011-08-15 | Basell Polyolefine Gmbh | Verfahren zur polymerisation von buten-1 |
WO2002100909A1 (en) | 2001-06-12 | 2002-12-19 | Basell Polyolefine Gmbh | Process for the polymerization of 1-butene |
US7511104B2 (en) | 2001-06-20 | 2009-03-31 | Exxonmobil Chemical Patents Inc. | Polyolefins made by catalyst comprising a noncoordinating anion and articles comprising them |
JP4418228B2 (ja) | 2001-06-22 | 2010-02-17 | バーゼル・ポリオレフィン・ゲーエムベーハー | メタロセン、オレフィンポリマー製造用の触媒系における使用 |
JP2005522406A (ja) | 2001-06-29 | 2005-07-28 | エクソンモービル・ケミカル・パテンツ・インク | メタロセン及び該メタロセン由来の触媒組成物 |
JP2004535505A (ja) | 2001-07-17 | 2004-11-25 | バセル ポリオレフィン ジーエムビーエイチ | オレフィン(共)重合のための多工程方法 |
US7019157B2 (en) | 2001-08-06 | 2006-03-28 | Chisso Corporation | Metallocene compounds, production process for olefin polymers using catalysts containing them and olefin polymers produced by the production process |
US7166683B2 (en) | 2001-11-12 | 2007-01-23 | Basell Polyolefine Gmbh | Process for polymerizing 1-butene and 1-butene polymers |
EP1448624A1 (de) | 2001-11-27 | 2004-08-25 | Basell Polyolefine GmbH | Verfahren zur herstellung von polymerzusammensetzungen |
EP1448578B1 (de) | 2001-11-30 | 2006-07-26 | Basell Polyolefine GmbH | Metallocene und verfahren zur herstellung von propylenpolymeren |
CA2368724C (en) | 2002-01-21 | 2011-06-14 | Bayer Inc. | Process for preparing isobutylene-based polymers |
JP2005517773A (ja) | 2002-02-25 | 2005-06-16 | バセル ポリオレフィン ジーエムビーエイチ | エチレンの共重合方法 |
US6995279B2 (en) | 2002-08-02 | 2006-02-07 | Chisso Corporation | Metallocene compounds, processes for the production of olefin polymers using catalysts containing the compounds, and olefin polymers produced by the processes |
WO2004022613A1 (en) | 2002-09-06 | 2004-03-18 | Basell Polyolefine Gmbh | Process for the copolymerization of ethylene |
US7943700B2 (en) | 2002-10-01 | 2011-05-17 | Exxonmobil Chemical Patents Inc. | Enhanced ESCR of HDPE resins |
US7569647B2 (en) | 2002-10-10 | 2009-08-04 | Basell Polyolefine Gmbh | Process for the copolymerization of ethylene |
US7223822B2 (en) | 2002-10-15 | 2007-05-29 | Exxonmobil Chemical Patents Inc. | Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom |
US7700707B2 (en) | 2002-10-15 | 2010-04-20 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions and articles made therefrom |
WO2004046214A2 (en) | 2002-10-15 | 2004-06-03 | Exxonmobil Chemical Patents Inc. | Multiple catalyst system for olefin polymerization and polymers produced therefrom |
US20040102311A1 (en) | 2002-11-21 | 2004-05-27 | Abbas Razavi | Bridged metallocene catalyst component, method of making, polyolefin catalyst having C1, C2, or Cs symmetry, methods of making, methods of polymerizing, olefins and products made thereof |
US7589160B2 (en) | 2002-12-04 | 2009-09-15 | Basell Polyolefine Gmbh | Process for preparing 1-butene polymers |
DE60329523D1 (de) | 2002-12-04 | 2009-11-12 | Basell Polyolefine Gmbh | 1-Buten-Copolymere und Herstellungsverfahren dafür |
US7195806B2 (en) | 2003-01-17 | 2007-03-27 | Fina Technology, Inc. | High gloss polyethylene articles |
EP1611169B1 (de) | 2003-03-21 | 2010-06-02 | Dow Global Technologies Inc. | Verfahren zur herstellung von polyolefinen mit kontrollierter morphologie |
WO2004099225A1 (en) | 2003-05-08 | 2004-11-18 | Basell Polyolefine Gmbh | Process for the production of halide metallocene compounds |
JP4771938B2 (ja) | 2003-05-12 | 2011-09-14 | バーゼル・ポリオレフィン・ゲーエムベーハー | 1−ブテンの重合方法 |
US7037989B2 (en) | 2003-05-27 | 2006-05-02 | Exxonmobil Chemical Patents Inc. | Copolymers of ethylene and/or α-olefins and vicinally disubstituted olefins |
CN101163723B (zh) | 2003-07-04 | 2010-12-22 | 巴塞尔聚烯烃股份有限公司 | 烯烃聚合方法 |
US8946329B2 (en) | 2003-08-25 | 2015-02-03 | Dow Global Technologies Llc | Coating compositions |
TW200517426A (en) | 2003-08-25 | 2005-06-01 | Dow Global Technologies Inc | Aqueous dispersion, its production method, and its use |
US7947776B2 (en) | 2003-08-25 | 2011-05-24 | Dow Global Technologies Llc | Aqueous dispersion, its production method, and its use |
US9169406B2 (en) | 2003-08-25 | 2015-10-27 | Dow Global Technologies Llc | Coating compositions |
US20100029164A1 (en) | 2008-08-04 | 2010-02-04 | Sudhin Datta | Soft Polypropylene-Based Nonwovens |
US9018112B2 (en) | 2003-11-18 | 2015-04-28 | Exxonmobil Chemicals Patents Inc. | Extensible polypropylene-based nonwovens |
DE602004018682D1 (de) | 2003-12-22 | 2009-02-05 | Basell Polyolefine Gmbh | Metallocenverbindungen |
WO2005095473A1 (en) | 2004-03-12 | 2005-10-13 | Basell Polyolefine Gmbh | Process for polymerizing 1-hexene or higher alpha-olefins |
WO2005095474A1 (en) | 2004-03-12 | 2005-10-13 | Basell Polyolefine Gmbh | Process for polymerizing 1-hexene or higher alpha-olefins |
WO2005105865A1 (en) | 2004-05-04 | 2005-11-10 | Basell Polyolefine Gmbh | Process for the preparation of atactic 1-butene polymers |
GB0411119D0 (en) | 2004-05-19 | 2004-06-23 | Exxonmobil Chem Patents Inc | Modifiers for thermoplastic alloys produced using such modifiers |
GB0411742D0 (en) | 2004-05-26 | 2004-06-30 | Exxonmobil Chem Patents Inc | Transition metal compounds for olefin polymerization and oligomerization |
PL1753813T3 (pl) | 2004-06-08 | 2008-03-31 | Basell Poliolefine Italia Srl | Kompozycja poliolefinowa mająca wysokie zrównoważenie sztywności, udarności i wydłużenia przy zerwaniu oraz niskiego skurczu termicznego |
US8003743B2 (en) | 2004-07-13 | 2011-08-23 | Basell Poliolefine Italia, s.r.l. | Metallocene compounds, ligands used in their preparation, preparation of 1-butene polymers and 1-butene polymers therefrom |
KR20070043798A (ko) | 2004-07-22 | 2007-04-25 | 바젤 폴리올레핀 게엠베하 | 분획가능한 1-부텐 중합체의 제조방법 |
JP2008506824A (ja) | 2004-07-22 | 2008-03-06 | バーゼル・ポリオレフィン・ゲーエムベーハー | 1−ブテンポリマー組成物 |
KR101229293B1 (ko) | 2004-10-18 | 2013-02-05 | 바셀 폴리올레핀 이탈리아 에스.알.엘 | 이소탁틱도가 낮은 부텐-1 (공)중합체 |
CN101044172B (zh) | 2004-10-21 | 2010-09-29 | 巴塞尔聚烯烃股份有限公司 | 1-丁烯聚合物及其制备方法 |
EP1655314A1 (de) | 2004-11-09 | 2006-05-10 | Basell Polyolefine GmbH | Polymerisationsverfahren von 1-buten mit propen |
JP2008520793A (ja) | 2004-11-22 | 2008-06-19 | バーゼル・ポリオレフィン・ゲーエムベーハー | プロピレンベースのターポリマー |
US7588706B2 (en) | 2004-12-16 | 2009-09-15 | Exxonmobil Chemical Patents Inc. | Multi-layer films with improved properties |
RU2405007C2 (ru) | 2004-12-17 | 2010-11-27 | Дау Глобал Текнолоджиз Инк. | Реологически модифицированные, имеющие относительно высокую прочность расплава полиэтиленовые композиции и способы изготовления труб, пленок, листов и изделий, формованных раздувом |
ATE502080T1 (de) | 2005-02-03 | 2011-04-15 | Basell Polyolefine Gmbh | Verfahren zur herstellung von warmgeformten artikeln |
WO2006097500A1 (en) | 2005-03-18 | 2006-09-21 | Basell Polyolefine Gmbh | Metallocene compounds |
AU2006224576B2 (en) | 2005-03-18 | 2011-11-03 | Basell Polyolefine Gmbh | Metallocene compounds |
BRPI0612170B1 (pt) | 2005-03-23 | 2017-02-21 | Basell Polyolefine Gmbh | processo para a polimerização de olefinas |
WO2006100258A1 (en) | 2005-03-23 | 2006-09-28 | Basell Polyolefine Gmbh | Process for the polymerization of olefins |
JP2008540714A (ja) | 2005-05-03 | 2008-11-20 | バーゼル・ポリオレフィン・ゲーエムベーハー | α−オレフィンの重合方法 |
ES2357363T3 (es) | 2005-05-10 | 2011-04-25 | Ineos Europe Limited | Nuevos copolímeros. |
WO2006120177A2 (en) | 2005-05-11 | 2006-11-16 | Basell Poliolefine Itatia S.R.L. | Polymerization process for preparing polyolefin blends |
EP1731536A1 (de) | 2005-06-09 | 2006-12-13 | Innovene Manufacturing France SAS | Unterstützte Polymerisationskatalysatoren |
CN101291986B (zh) | 2005-10-21 | 2011-12-14 | 巴塞尔聚烯烃股份有限公司 | 用于注射模塑的聚丙烯 |
WO2007045603A1 (en) | 2005-10-21 | 2007-04-26 | Basell Polyolefine Gmbh | Propylene polymers |
ES2721552T3 (es) | 2005-10-25 | 2019-08-01 | Gen Cable Technologies Corp | Composiciones de aislamiento libres de plomo mejoradas que contienen polímeros de metaloceno |
EP1963347B1 (de) | 2005-12-14 | 2011-10-19 | ExxonMobil Chemical Patents Inc. | Halogensubstituierte metallocenverbindungen für die olefinpolymerisation |
EP1803747A1 (de) | 2005-12-30 | 2007-07-04 | Borealis Technology Oy | Oberflächemodifizierte Polymerisationskatalysatoren zur Herstellung von Polyolefinfilmen mit niedrigem Gelgehalt |
US8343602B2 (en) | 2006-02-23 | 2013-01-01 | Basell Poliolefine Italia, s.r.l. | Propylene polymers for injection molding applications |
ATE526337T1 (de) | 2006-03-17 | 2011-10-15 | Basell Polyolefine Gmbh | Metallocenverbindungen |
JP2009533382A (ja) | 2006-04-12 | 2009-09-17 | バーゼル・ポリオレフィン・ゲーエムベーハー | メタロセン化合物 |
EP2010579A1 (de) | 2006-04-21 | 2009-01-07 | Basell Polyolefine GmbH | Verfahren zur herstellung von ethylen-propylen-copolymeren |
US8742042B2 (en) | 2006-04-21 | 2014-06-03 | Basell Polyolefine Gmbh | Process for the preparation of ethylene copolymers |
BRPI0706040B1 (pt) | 2006-05-02 | 2018-03-06 | Dow Global Technologies Inc. | Encapamento de cabo de força ou comunicação, e método para produzir um encapamento de cabo de força ou comunicação |
US7456244B2 (en) | 2006-05-23 | 2008-11-25 | Dow Global Technologies | High-density polyethylene compositions and method of making the same |
GB0610667D0 (en) | 2006-05-30 | 2006-07-05 | Nova Chem Int Sa | Supported polymerization catalysts |
KR101423946B1 (ko) | 2006-08-30 | 2014-08-01 | 바젤 폴리올레핀 게엠베하 | 1-부텐 프로필렌 공중합체 조성물 |
JP5580589B2 (ja) | 2006-08-30 | 2014-08-27 | バーゼル・ポリオレフィン・ゲーエムベーハー | 1−ブテンプロピレンコポリマー組成物 |
US7985804B2 (en) | 2006-11-06 | 2011-07-26 | Exxonmobil Chemical Patents Inc. | Rubber toughened compositions, articles, films, and methods of making the same |
US8309659B2 (en) | 2006-12-20 | 2012-11-13 | Basell Poliolefine Italia S.R.L. | Filled polyolefin compositions |
US8143352B2 (en) | 2006-12-20 | 2012-03-27 | Exxonmobil Research And Engineering Company | Process for fluid phase in-line blending of polymers |
EP2121829B1 (de) | 2006-12-20 | 2012-02-01 | Basell Poliolefine Italia S.r.l. | Polypropylenzusammensetzungen mit füllern und/oder pigmenten |
US8227550B2 (en) | 2006-12-20 | 2012-07-24 | Basell Poliolefine Italia S.R.L. | Filled polyolefin compositions |
KR20100014214A (ko) | 2007-05-02 | 2010-02-10 | 다우 글로벌 테크놀로지스 인크. | 고-밀도 폴리에틸렌 조성물, 그의 제조 방법, 그로부터 만들어진 사출 성형 물품, 및 이러한 물품의 제조 방법 |
PL2158235T3 (pl) | 2007-06-25 | 2011-04-29 | Basell Polyolefine Gmbh | Kopolimery 1-buten-etylen |
US7981517B2 (en) | 2007-08-28 | 2011-07-19 | Dow Global Technologies Inc. | Bituminous compositions and methods of making and using same |
TW200932762A (en) | 2007-10-22 | 2009-08-01 | Univation Tech Llc | Polyethylene compositions having improved properties |
US7906588B2 (en) | 2007-10-26 | 2011-03-15 | Exxonmobil Chemical Patents Inc. | Soft heterogeneous isotactic polypropylene compositions |
WO2009082451A2 (en) | 2007-12-18 | 2009-07-02 | Univation Technologies, Llc | Method for controlling bimodal catalyst activity during polymerization |
WO2009080438A1 (en) | 2007-12-20 | 2009-07-02 | Basell Polyolefine Gmbh | Process for obtaining polymers of ethylene and cycloolefins |
JP2011515518A (ja) | 2008-03-20 | 2011-05-19 | バーゼル・ポリオレフィン・イタリア・ソチエタ・ア・レスポンサビリタ・リミタータ | 1−ブテン系ポリマー類の組成物類 |
EP2274347B1 (de) | 2008-04-22 | 2011-10-05 | Basell Poliolefine Italia S.r.l. | 1-butenterpolymere |
US9938400B2 (en) | 2008-04-23 | 2018-04-10 | Exxonmobil Chemical Patents Inc. | Propylene copolymers in soft thermoplastic blends |
EP2133367A1 (de) | 2008-06-09 | 2009-12-16 | INEOS Manufacturing Belgium NV | Neuartige Copolymere |
US8242198B2 (en) | 2008-06-09 | 2012-08-14 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions |
US9498932B2 (en) | 2008-09-30 | 2016-11-22 | Exxonmobil Chemical Patents Inc. | Multi-layered meltblown composite and methods for making same |
US9168718B2 (en) | 2009-04-21 | 2015-10-27 | Exxonmobil Chemical Patents Inc. | Method for producing temperature resistant nonwovens |
US10161063B2 (en) | 2008-09-30 | 2018-12-25 | Exxonmobil Chemical Patents Inc. | Polyolefin-based elastic meltblown fabrics |
EP2172490A1 (de) | 2008-10-03 | 2010-04-07 | Ineos Europe Limited | Polimerisationsverfahren |
EP2177548A1 (de) | 2008-10-14 | 2010-04-21 | Ineos Europe Limited | Copolymere und Folien daraus |
WO2010068045A2 (ko) | 2008-12-11 | 2010-06-17 | 주식회사 엘지화학 | 혼성 담지 메탈로센 촉매, 이의 제조방법 및 이를 이용한 올레핀계 중합체의 제조방법 |
ES2408589T3 (es) | 2008-12-18 | 2013-06-21 | Univation Technologies, Llc | Método para tratamiento de un lecho de siembra para una reacción de polimerización |
JP2012512919A (ja) | 2008-12-19 | 2012-06-07 | バーゼル・ポリオレフィン・イタリア・ソチエタ・ア・レスポンサビリタ・リミタータ | ポリオレフィン繊維 |
EP2358810B1 (de) | 2008-12-19 | 2013-02-27 | Basell Poliolefine Italia S.r.l. | Gefüllte polyolefinzusammensetzungen |
KR101235390B1 (ko) * | 2009-01-12 | 2013-02-20 | 주식회사 엘지화학 | 전이금속 화합물을 포함하는 올레핀 중합용 촉매 조성물 및 이를 이용한 고내열 올레핀 중합체의 제조방법 |
EP2379609B1 (de) | 2009-01-13 | 2012-10-24 | Basell Polyolefine GmbH | Polyethylen-copolymere |
EP2376568B1 (de) | 2009-01-13 | 2013-05-08 | Basell Poliolefine Italia S.r.l. | Polymerzusammensetzung |
BRPI1005286A2 (pt) | 2009-01-30 | 2016-07-05 | Dow Global Technologies Llc | composição de polietileno de alta densidade, método para produzir uma composição de polietileno de alta densidade, dispositivo de fechamento e método para produzir um dispositivo de fechamento |
CN102395464A (zh) | 2009-02-27 | 2012-03-28 | 埃克森美孚化学专利公司 | 具有非弹性区的双轴弹性非织造层压体 |
US8378042B2 (en) | 2009-04-28 | 2013-02-19 | Exxonmobil Chemical Patents Inc. | Finishing process for amorphous polymers |
US9127151B2 (en) | 2009-04-28 | 2015-09-08 | Exxonmobil Chemical Patents Inc. | Polymer compositions having improved properties as viscosity index improvers and use thereof in lubricating oils |
US20120028865A1 (en) | 2010-07-28 | 2012-02-02 | Sudhin Datta | Viscosity Modifiers Comprising Blends of Ethylene-Based Copolymers |
JP2013506062A (ja) | 2009-10-02 | 2013-02-21 | エクソンモービル・ケミカル・パテンツ・インク | 多層メルトブローン複合材料及びその製造方法 |
WO2011061151A1 (en) | 2009-11-17 | 2011-05-26 | Basell Polyolefine Gmbh | Ethylene copolymers |
EP2357035A1 (de) | 2010-01-13 | 2011-08-17 | Ineos Europe Limited | Polymerpulveraufbewahrungs- und/oder -transport- und/oder -entgasungsgefäßen |
EP2348057A1 (de) | 2010-01-21 | 2011-07-27 | INEOS Manufacturing Belgium NV | Neuartige Polymere |
CN102712720B (zh) | 2010-01-22 | 2014-12-31 | 埃克森美孚化学专利公司 | 乙烯共聚物、其制备方法以及应用 |
US8378048B2 (en) | 2010-01-27 | 2013-02-19 | Exxonmobil Chemical Patents Inc. | Copolymers, compositions thereof, and methods for making them |
US8058461B2 (en) | 2010-03-01 | 2011-11-15 | Exxonmobil Chemical Patents Inc. | Mono-indenyl transition metal compounds and polymerization therewith |
CN102791481B (zh) | 2010-03-12 | 2015-07-08 | 埃克森美孚化学专利公司 | 弹性熔喷层压体构造及其制造方法 |
EP2383301A1 (de) | 2010-04-30 | 2011-11-02 | Ineos Europe Limited | Polymerisierungsverfahren |
EP2383298A1 (de) | 2010-04-30 | 2011-11-02 | Ineos Europe Limited | Polymerisierungsverfahren |
CN102958997B (zh) | 2010-06-29 | 2016-05-11 | 巴塞尔聚烯烃意大利有限责任公司 | 填充的聚烯烃组合物 |
GB201012273D0 (en) | 2010-07-22 | 2010-09-08 | Ineos Mfg Belguim Nv | Polymer compositon |
EP2410011A1 (de) | 2010-07-23 | 2012-01-25 | INEOS Manufacturing Belgium NV | Polyethylenzusammensetzung |
CN103025818B (zh) | 2010-07-28 | 2015-06-17 | 埃克森美孚化学专利公司 | 含乙烯-基共聚物的共混物的粘度改性剂 |
WO2012015572A1 (en) | 2010-07-28 | 2012-02-02 | Exxonmobil Chemical Patents Inc. | Viscosity modifiers comprising blends of ethylene-based copolymers |
SG186167A1 (en) | 2010-07-28 | 2013-01-30 | Exxonmobil Chem Patents Inc | Ethylene based copolymer compositions as viscosity modifiers and methods for making them |
CN103328518B (zh) | 2010-11-29 | 2016-07-06 | 英力士销售(英国)有限公司 | 聚合控制方法 |
EP2465876A1 (de) | 2010-12-15 | 2012-06-20 | INEOS Manufacturing Belgium NV | Aktivierung von Trägern |
JP6457716B2 (ja) | 2011-01-14 | 2019-01-23 | ダブリュー・アール・グレイス・アンド・カンパニー−コネチカット | 修飾メタロセン触媒の作成法、生成された触媒およびそれらの使用 |
US9012359B2 (en) | 2011-01-20 | 2015-04-21 | Ineos Sales (Uk) Limited | Activating supports |
US9248630B2 (en) | 2011-04-08 | 2016-02-02 | Ineos Europe Ag | Laminate comprising a polyolefin layer adhered to a base layer |
BR112013033155B1 (pt) | 2011-06-24 | 2020-12-22 | Ineos Europe Ag | Processo de pasta fluida para a polimerização de etileno em um sistema de reator e uso de propano como um diluente e uma concentração de sólidos |
US8383740B1 (en) | 2011-08-12 | 2013-02-26 | Ineos Usa Llc | Horizontal agitator |
EP2768870B1 (de) | 2011-10-17 | 2018-01-10 | Ineos Europe AG | Verfahrenssteuerung zur polymerentgasung |
EP2785786B1 (de) | 2011-12-01 | 2018-05-30 | Ineos Europe AG | Polymermischungen |
IN2014CN04332A (de) | 2011-12-14 | 2015-09-04 | Ineos Europe Ag | |
EP2606970A1 (de) | 2011-12-19 | 2013-06-26 | Basell Polyolefine GmbH | Monocyclopentadienyl zweikernige Komplexe, bei ihrer Herstellung verwendete Liganden, Katalysatorsysteme und Verfahren zur Olefin-Polymerisation |
CN104205245B (zh) | 2012-01-26 | 2020-06-23 | 英尼奥斯欧洲股份公司 | 用于电线和电缆应用的共聚物 |
US9139794B2 (en) | 2012-02-03 | 2015-09-22 | Exxonmobil Chemical Patents Inc. | Process for the production of polymeric compositions useful as oil modifiers |
US10316176B2 (en) | 2012-02-03 | 2019-06-11 | Exxonmobil Chemical Patents Inc. | Polymer compositions and methods of making them |
WO2013115912A1 (en) | 2012-02-03 | 2013-08-08 | Exxonmobil Chemical Patents Inc. | Process for the production of polymeric compositions useful as oil modifiers |
EP2676972A1 (de) | 2012-06-19 | 2013-12-25 | Basell Polyolefine GmbH | Verfahren zum Erhalt einer Polyolefinzusammensetzung |
EP2743000A1 (de) | 2012-12-13 | 2014-06-18 | Basell Poliolefine Italia S.r.l. | Katalysatorsystem zur Herstellung von Polyolefinen |
ITMI20122201A1 (it) | 2012-12-20 | 2014-06-21 | Versalis Spa | Complesso osso-azotato di cobalto, sistema catalitico comprendente detto complesso osso-azotato e procedimento per la (co)polimerizzazione di dieni coniugati |
ITMI20122199A1 (it) | 2012-12-20 | 2014-06-21 | Versalis Spa | Procedimento per la preparazione di (co)polimeri di dieni coniugati in presenza di un sistema catalitico comprendente un complesso bis-imminico di cobalto |
ITMI20122203A1 (it) | 2012-12-20 | 2014-06-21 | Versalis Spa | Procedimento per la preparazione di (co)polimeri di dieni coniugati in presenza di un sistema catalitico comprendente un complesso osso-azotato di cobalto |
ITMI20122206A1 (it) | 2012-12-20 | 2014-06-21 | Versalis Spa | Procedimento per la preparazione di (co)polimeri di dieni coniugati in presenza di un sistema catalitico comprendente un complesso bis-immino-piridinico di cobalto |
KR102177644B1 (ko) | 2012-12-28 | 2020-11-11 | 다우 글로벌 테크놀로지스 엘엘씨 | 코팅 조성물 및 그로부터 제조된 물품 |
WO2014105614A1 (en) | 2012-12-28 | 2014-07-03 | Univation Technologies, Llc | Methods of integrating aluminoxane production into catalyst production |
EP2922925B1 (de) | 2012-12-28 | 2019-12-04 | Dow Global Technologies LLC | Beschichtungszusammensetzungen |
RU2647855C2 (ru) | 2013-01-14 | 2018-03-21 | ЮНИВЕЙШН ТЕКНОЛОДЖИЗ, ЭлЭлСи | Способы получения каталитических систем с повышенной производительностью |
US10548367B2 (en) | 2013-01-29 | 2020-02-04 | Exxonmobil Chemical Patents Inc. | Footwear sole comprising a propylene-based elastomer, footwear comprising said sole, and methods of making them |
EP2767542A1 (de) | 2013-02-18 | 2014-08-20 | Basell Polyolefine GmbH | Oligomerisierungskatalysator |
ITMI20131828A1 (it) | 2013-11-05 | 2015-05-06 | Versalis Spa | Polibutadieni di-blocco stereoregolari a struttura 1,4-cis/1,2 sindiotattica da polimerizzazione stereospecifica |
ITMI20131830A1 (it) | 2013-11-05 | 2015-05-06 | Versalis Spa | Polibutadieni di-blocco stereoregolari a struttura 1,4-cis/1,2 sindiotattica da polimerizzazione stereospecifica |
US10059724B2 (en) | 2014-09-17 | 2018-08-28 | Versalis S.P.A. | Pyridine complex of zirconium, catalytic system comprising said pyridine complex of zirconium and process of (co)polymerization of conjugated dienes |
CN107108777B (zh) | 2014-11-12 | 2021-02-05 | 埃克森美孚化学专利公司 | 增塑剂的纯化及其在聚合物生产方法和装置中的用途 |
CA2967660C (en) | 2014-11-25 | 2023-05-02 | Univation Technologies, Llc | Methods of controlling polyolefin melt index |
CN107660216B (zh) | 2015-05-08 | 2021-05-14 | 埃克森美孚化学专利公司 | 聚合方法 |
EP4321564A3 (de) | 2015-07-09 | 2024-04-24 | Ineos Europe AG | Copolymere und folien daraus |
ITUB20152581A1 (it) | 2015-07-29 | 2017-01-29 | Versalis Spa | Complesso azotato di titanio, sistema catalitico comprendente detto complesso azotato di titanio e procedimento per la (co)polimerizzazione di dieni coniugati |
ITUA20163932A1 (it) | 2016-05-30 | 2017-11-30 | Versalis Spa | Complesso osso-azotato di ferro, sistema catalitico comprendente detto complesso osso-azotato di ferro e procedimento per la (co)polimerizzazione di dieni coniugati |
WO2018063764A1 (en) | 2016-09-27 | 2018-04-05 | Exxonmobil Chemical Patents Inc. | Polymerization process |
WO2018063765A1 (en) | 2016-09-27 | 2018-04-05 | Exxonmobil Chemical Patents Inc. | Polymerization process |
WO2018063767A1 (en) | 2016-09-27 | 2018-04-05 | Exxonmobil Chemical Patents Inc. | Polymerization process |
WO2018118155A1 (en) | 2016-12-20 | 2018-06-28 | Exxonmobil Chemical Patents Inc. | Polymerization process |
WO2019027524A1 (en) | 2017-08-02 | 2019-02-07 | Exxonmobil Chemical Patents Inc. | MULTILAYER FILMS AND METHODS OF MANUFACTURE |
IT201700109176A1 (it) | 2017-09-29 | 2019-03-29 | Versalis Spa | Complesso bis-imminico di titanio, sistema catalitico comprendente detto complesso bis-imminico di titanio e procedimento per la (co)polimerizzazione di dieni coniugati |
US11518824B2 (en) | 2017-10-11 | 2022-12-06 | Basell Polyolefine Gmbh | Supported catalyst system |
WO2019118073A1 (en) | 2017-12-13 | 2019-06-20 | Exxonmobil Chemical Patents Inc. | Deactivation methods for active components from gas phase polyolefin polymerization process |
WO2019157002A1 (en) * | 2018-02-06 | 2019-08-15 | Northwestern University | Highly branched, low molecular weight polyolefins and methods for their production |
WO2019173030A1 (en) | 2018-03-08 | 2019-09-12 | Exxonmobil Chemical Patents Inc. | Methods of preparing and monitoring a seed bed for polymerization reactor startup |
US11459408B2 (en) | 2018-05-02 | 2022-10-04 | Exxonmobil Chemical Patents Inc. | Methods for scale-up from a pilot plant to a larger production facility |
US11447587B2 (en) | 2018-05-02 | 2022-09-20 | Exxonmobil Chemical Patents Inc. | Methods for scale-up from a pilot plant to a larger production facility |
ES2970673T3 (es) | 2018-06-13 | 2024-05-30 | Exxonmobil Chemical Patents Inc | Composiciones de mezclas de poliolefinas |
CN112384542A (zh) | 2018-06-28 | 2021-02-19 | 埃克森美孚化学专利公司 | 聚乙烯组合物、电线和电缆及其制备方法 |
WO2020014138A1 (en) | 2018-07-09 | 2020-01-16 | Exxonmobil Chemical Patents Inc. | Polyethylene cast films and methods for making the same |
EP3826833A1 (de) | 2018-07-26 | 2021-06-02 | ExxonMobil Chemical Patents Inc. | Mehrlagige schaumstofffolien und verfahren zur herstellung davon |
WO2020056119A1 (en) | 2018-09-14 | 2020-03-19 | Fina Technology, Inc. | Polyethylene and controlled rheology polypropylene polymer blends and methods of use |
US20220025135A1 (en) | 2018-11-13 | 2022-01-27 | Exxonmobil Chemical Patents Inc. | Polyethylene Films |
US11649331B2 (en) | 2018-11-13 | 2023-05-16 | Exxonmobil Chemical Patents Inc. | Polyethylene blends and films |
WO2020163079A1 (en) | 2019-02-06 | 2020-08-13 | Exxonmobil Chemical Patents Inc. | Films and backsheets for hygiene articles |
CA3121960A1 (en) | 2019-02-20 | 2020-08-27 | Fina Technology, Inc. | Polymer compositions with low warpage |
WO2021080813A1 (en) | 2019-10-22 | 2021-04-29 | Exxonmobil Chemical Patents Inc. | Thermoplastic vulcanizate compositions and processes for the production thereof |
WO2021126458A1 (en) | 2019-12-17 | 2021-06-24 | Exxonmobil Chemical Patents Inc. | Films made of polyethylene blends for improved sealing performance and mechanical properties |
WO2021183337A1 (en) | 2020-03-12 | 2021-09-16 | Exxonmobil Chemical Patents Inc. | Films made of polyethylene blends for improved bending stiffness and high md tear resistance |
CA3214562A1 (en) | 2021-04-26 | 2022-11-03 | Michael Mcleod | Thin single-site catalyzed polymer sheets |
EP4330294A1 (de) | 2021-04-30 | 2024-03-06 | ExxonMobil Chemical Patents Inc. | Verfahren zum übergang zwischen verschiedenen polymerisationskatalysatoren in einem polymerisationsreaktor |
WO2023114815A1 (en) | 2021-12-17 | 2023-06-22 | Exxonmobil Chemical Patents Inc. | Processes for making polyolefins with composition control |
WO2023117512A1 (en) | 2021-12-23 | 2023-06-29 | Basell Poliolefine Italia S.R.L. | Soft polyolefin composition |
WO2024073260A1 (en) | 2022-09-28 | 2024-04-04 | Exxonmobil Chemical Patents Inc. | Ethylene copolymers for photovoltaic cells |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0780930B2 (ja) * | 1985-12-26 | 1995-08-30 | 三井石油化学工業株式会社 | α−オレフインの重合方法 |
IL85097A (en) * | 1987-01-30 | 1992-02-16 | Exxon Chemical Patents Inc | Catalysts based on derivatives of a bis(cyclopentadienyl)group ivb metal compound,their preparation and their use in polymerization processes |
US5384299A (en) † | 1987-01-30 | 1995-01-24 | Exxon Chemical Patents Inc. | Ionic metallocene catalyst compositions |
NZ235032A (en) † | 1989-08-31 | 1993-04-28 | Dow Chemical Co | Constrained geometry complexes of titanium, zirconium or hafnium comprising a substituted cyclopentadiene ligand; use as olefin polymerisation catalyst component |
US5064802A (en) * | 1989-09-14 | 1991-11-12 | The Dow Chemical Company | Metal complex compounds |
CA2024830A1 (en) † | 1989-09-29 | 1991-03-30 | Richard E. Campbell, Jr. | Process for preparation of syndiotactic vinyl aromatic polymers |
-
1991
- 1991-06-21 DE DE0551277T patent/DE551277T1/de active Pending
- 1991-06-21 RU RU92016448A patent/RU2118203C1/ru not_active IP Right Cessation
- 1991-06-21 DE DE69122275T patent/DE69122275T3/de not_active Expired - Lifetime
- 1991-06-21 DK DK91912554T patent/DK0551277T4/da active
- 1991-06-21 EP EP91912554A patent/EP0551277B2/de not_active Expired - Lifetime
- 1991-06-21 ES ES95200999T patent/ES2092913T5/es not_active Expired - Lifetime
- 1991-06-21 JP JP3511782A patent/JP2954351B2/ja not_active Expired - Lifetime
- 1991-06-21 DE DE69124255T patent/DE69124255T3/de not_active Expired - Lifetime
- 1991-06-21 AT AT91912554T patent/ATE147761T1/de not_active IP Right Cessation
- 1991-06-21 BR BR919106589A patent/BR9106589A/pt not_active IP Right Cessation
- 1991-06-21 KR KR1019920703315A patent/KR0123370B1/ko not_active IP Right Cessation
- 1991-06-21 EP EP95200999A patent/EP0672688B2/de not_active Expired - Lifetime
- 1991-06-21 WO PCT/US1991/004390 patent/WO1992000333A2/en active IP Right Grant
- 1991-06-21 EP EP95200997A patent/EP0670334A3/de not_active Withdrawn
- 1991-06-21 EP EP95200998A patent/EP0672689A1/de not_active Withdrawn
- 1991-06-21 CA CA002085581A patent/CA2085581C/en not_active Expired - Fee Related
- 1991-06-21 ES ES91912554T patent/ES2079330T5/es not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
DE69124255D1 (de) | 1997-02-27 |
EP0670334A2 (de) | 1995-09-06 |
DK0551277T3 (da) | 1997-07-14 |
KR0123370B1 (ko) | 1997-11-12 |
BR9106589A (pt) | 1993-06-01 |
DE69124255T2 (de) | 1997-06-05 |
ES2079330T3 (es) | 1997-03-01 |
WO1992000333A3 (en) | 1992-03-19 |
ES2079330T1 (es) | 1996-01-16 |
KR930701493A (ko) | 1993-06-11 |
EP0551277B1 (de) | 1997-01-15 |
EP0551277B2 (de) | 2005-03-09 |
EP0672689A1 (de) | 1995-09-20 |
ES2092913T5 (es) | 2002-10-16 |
RU2118203C1 (ru) | 1998-08-27 |
DE69122275T3 (de) | 2002-10-31 |
CA2085581A1 (en) | 1991-12-23 |
JPH05507756A (ja) | 1993-11-04 |
EP0551277A1 (de) | 1993-07-21 |
ES2079330T5 (es) | 2005-10-01 |
DE69122275D1 (de) | 1996-10-24 |
DE69122275T2 (de) | 1997-05-15 |
WO1992000333A2 (en) | 1992-01-09 |
DE551277T1 (de) | 1996-10-10 |
ATE147761T1 (de) | 1997-02-15 |
ES2092913T3 (es) | 1996-12-01 |
DE69124255T3 (de) | 2005-10-06 |
EP0672688B2 (de) | 2002-04-17 |
EP0670334A3 (de) | 1995-09-13 |
DK0551277T4 (da) | 2005-04-04 |
JP2954351B2 (ja) | 1999-09-27 |
CA2085581C (en) | 2002-07-30 |
EP0672688A1 (de) | 1995-09-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0672688B1 (de) | Aluminiumfreie Monocyclopentadienyl-Metallocenkatalysatoren für Olefinpolymerisation | |
US7163907B1 (en) | Aluminum-free monocyclopentadienyl metallocene catalysts for olefin polymerization | |
EP0420436B1 (de) | Katalysatoren zur Polymerisation von Olefinen | |
EP0468537B1 (de) | Katalysatoren, Verfahren zur Herstellung derselben und Verfahren zu deren Anwendung | |
EP0548277B1 (de) | Verfahren zur herstellung kristalliner poly-alpha-olefine mit monozyklopentadienylkompex von übergangsmetallen | |
EP0640090B1 (de) | Verfahren zur herstellung von cyclopentadien-metallkomplex verbindungen und verfahren zur verwendung | |
US5621126A (en) | Monocyclopentadienyl metal compounds for ethylene-α-olefin-copolymer production catalysts | |
JP5793820B2 (ja) | 分枝ビニル末端ポリマー及びその製造方法 | |
US5955625A (en) | Monocyclopentadienyl metal compounds for ethylene-α-olefin-copolymer production catalysts | |
EP0766703B1 (de) | Monocyclopentadienyl-metalverbindungen als katalysatoren zur produktion von ethylen-alpha-olefincopolymeren | |
EP0705283B1 (de) | Verfahren zur herstellung von poly-alpha-olefinen mit monozyklopentadienylkomplexen von übergangsmetallen | |
US6160066A (en) | Monocyclopentadienyl metal compounds for ethylene-α-olefin-copolymer production catalysts | |
EP4159771A1 (de) | Gemischte katalytische zusammensetzung, katalysator damit und verfahren zur herstellung davon | |
CA2193883C (en) | Monocyclopentadienyl metal compounds for ethylene-.alpha.-olefin copolymer production catalysts | |
AU643237C (en) | Monocyclopentadienyl transition metal olefin polymerization catalysts |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19950418 |
|
AC | Divisional application: reference to earlier application |
Ref document number: 551277 Country of ref document: EP |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB IT LI NL SE |
|
17Q | First examination report despatched |
Effective date: 19951227 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
TCNL | Nl: translation of patent claims filed | ||
AC | Divisional application: reference to earlier application |
Ref document number: 551277 Country of ref document: EP |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE DE ES FR GB IT NL SE |
|
REF | Corresponds to: |
Ref document number: 69122275 Country of ref document: DE Date of ref document: 19961024 |
|
ITF | It: translation for a ep patent filed |
Owner name: BARZANO' E ZANARDO MILANO S.P.A. |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2092913 Country of ref document: ES Kind code of ref document: T3 |
|
ET | Fr: translation filed |
Free format text: CORRECTIONS |
|
RIN2 | Information on inventor provided after grant (corrected) |
Free format text: CANICH, JO ANN MARIE * HLATKY, GREGORY GEORGE * TURNER, HOWARD WILLIAM |
|
PLBQ | Unpublished change to opponent data |
Free format text: ORIGINAL CODE: EPIDOS OPPO |
|
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
PLBF | Reply of patent proprietor to notice(s) of opposition |
Free format text: ORIGINAL CODE: EPIDOS OBSO |
|
26 | Opposition filed |
Opponent name: THE DOW CHEMICAL COMPANY Effective date: 19970617 |
|
NLR1 | Nl: opposition has been filed with the epo |
Opponent name: THE DOW CHEMICAL COMPANY |
|
PLBF | Reply of patent proprietor to notice(s) of opposition |
Free format text: ORIGINAL CODE: EPIDOS OBSO |
|
PLBF | Reply of patent proprietor to notice(s) of opposition |
Free format text: ORIGINAL CODE: EPIDOS OBSO |
|
PLBQ | Unpublished change to opponent data |
Free format text: ORIGINAL CODE: EPIDOS OPPO |
|
PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |
|
R26 | Opposition filed (corrected) |
Opponent name: THE DOW CHEMICAL COMPANY Effective date: 19970617 |
|
NLR1 | Nl: opposition has been filed with the epo |
Opponent name: THE DOW CHEMICAL COMPANY |
|
PLAW | Interlocutory decision in opposition |
Free format text: ORIGINAL CODE: EPIDOS IDOP |
|
APAC | Appeal dossier modified |
Free format text: ORIGINAL CODE: EPIDOS NOAPO |
|
APAE | Appeal reference modified |
Free format text: ORIGINAL CODE: EPIDOS REFNO |
|
RAP2 | Party data changed (patent owner data changed or rights of a patent transferred) |
Owner name: EXXONMOBIL CHEMICAL PATENTS INC. |
|
NLT2 | Nl: modifications (of names), taken from the european patent patent bulletin |
Owner name: EXXONMOBIL CHEMICAL PATENTS INC. |
|
APAC | Appeal dossier modified |
Free format text: ORIGINAL CODE: EPIDOS NOAPO |
|
PLAW | Interlocutory decision in opposition |
Free format text: ORIGINAL CODE: EPIDOS IDOP |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PUAH | Patent maintained in amended form |
Free format text: ORIGINAL CODE: 0009272 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT MAINTAINED AS AMENDED |
|
27A | Patent maintained in amended form |
Effective date: 20020417 |
|
AK | Designated contracting states |
Kind code of ref document: B2 Designated state(s): BE DE ES FR GB IT NL SE |
|
NLR2 | Nl: decision of opposition | ||
ET3 | Fr: translation filed ** decision concerning opposition | ||
NLR3 | Nl: receipt of modified translations in the netherlands language after an opposition procedure | ||
REG | Reference to a national code |
Ref country code: ES Ref legal event code: DC2A Kind code of ref document: T5 Effective date: 20020529 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20050603 Year of fee payment: 15 |
|
APAH | Appeal reference modified |
Free format text: ORIGINAL CODE: EPIDOSCREFNO |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20060622 |
|
EUG | Se: european patent has lapsed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20100617 Year of fee payment: 20 Ref country code: ES Payment date: 20100618 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20100621 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20100607 Year of fee payment: 20 Ref country code: BE Payment date: 20100630 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20100401 Year of fee payment: 20 Ref country code: DE Payment date: 20100630 Year of fee payment: 20 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R071 Ref document number: 69122275 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R071 Ref document number: 69122275 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: V4 Effective date: 20110621 |
|
BE20 | Be: patent expired |
Owner name: *EXXONMOBIL CHEMICAL PATENTS INC. Effective date: 20110621 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: PE20 Expiry date: 20110620 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20110621 Ref country code: GB Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20110620 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20120220 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20110622 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20110622 |